N-substituted derivatives of 4, 4&#39;-diaminodiphenyl ether



Patentedsept. 18, 1945 .N-SUBSTITUTED psmva'rrvnsor 4.4-

pmumomrnnm rrrnnn.

Hans Z. Lecher, Plainfield, Robert P. Parker, Somerville, and John J. Denton, Bound Brook, N. J.,,assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine.

No Drawing. Application July 3, 1944,

' Serial No. 543,438

"6 Claims.

This invention relates to a new series of chemical compounds comprising organic derivatives of 4,4'-diaminodiphenyl ether useful as intermediates in the production of dyestufis. More particularly, the present invention relates to N-substituted derivatives of 4,4'-diaminodiphenyl ether represented by the following formula:

in which B is selected from the group consisting of para-nitrophenyl, para-aminophenyl, paraamino-ortho-sulfophenyl and salts of the latter two.

The amino derivatives are preferred as they have greater technical utility as bases for the production of azo dyestuffs particularly the produc- Example 1 NnQNO. OrNa To a solution of 60 parts of sodium 2-chloro- 5-nitrobenzene sulfonate in 420 parts of water are NOEQNH OzNa - added 63 parts of calcium carbonate and 21 parts tion of ice colors by tetrazotization and coupling with appropriate ice color coupling components. These ice colors are dyes with strong blue to violet shades of superiorfastness.

While the'present invention is not intended to be limited to a particular method of producing the new compounds, we prefer to use a method comprising the condensation of 4,4"-diaminodiphenyl ether with a ara-nitro-halogen 'benzene followed by reduction of nitro group to the amino group if the latter compound is desired. It is equally feasible toemploy a para-nitrohalogen benzene containing a negative substituent such as sulfonic acid group. The condensation under such circumstances takes place very rapidly but it is necessary'to hydrolyze oil the sulfonic acid group which can be efiected either before or after the reduction if the unsulfonated compound is desired. The reaction proceeds more smoothly when the reactants are dissolved in a solvent which in the case of nitrohalogen benzene containing a sulfonic acid group may be water. As hydrohalic acid is set free the presence of an acid binding agent is desirable such as a metal hydroxide, carbonate or the like. In some cases the use'of a cupriferous catalyst is of advantage. Reduction of nitro to the amino group may be carried out either by alkaline or acidic reducing agents- The pH will determine whether the free bases or salts are produced.

The invention will be described in greater detail in conjunction with the specific examples which are typical illustrations. The parts are by weight.

1 ether may be obtained chemically pure by crys of 4,4'-diaminodiphenyl ether. The reaction mixture is heated at reflux under an atmosphere of carbon dioxide until the reaction is complete. The reaction mixture is filtered at elevated temperature and the filtrate is chilled below room temperature. Hydrochloric acid is added until the solutionis acidic to Congo .red test paper.

After stirring for one hour, the precipitated material is removed by filtration and the filtrate is recovered. To this filtrate, soda ash is added mm the solution is alkaline to brilliant yellow. test paper." This solution is heated to C. and is clarified from a smallamount of calcium carbonate. The temperature of the filtrate is again lowered and-sodium chloride is added to complete precipitation. 1

The salted-out product is separated by filtration and the residue is washed on the filterwith ice water to remove brine. The disodium salt of 4 ,4-bis N-(2"-sulfo-4"-nitrophenyl) amino diphenyl ether may be rendered chemically pure by recrystallization from dilute methanol.

Example 2 6.5 parts of the product of Example 1 is ground into a thin slurry with parts of 25% hydrochloric acid. The slurry is transferred to a reaction vessel and is heated at gentle-reflux for 22 hours. It changes in color from 9; golden yellow to a deep red-orange. Thereaction mixture is cooled, and is diluted with 200 parts of water. The undissolved solid is collected on a filter, washed thoroughly with water, and dried.

4,4'-bis-N-(4"-nitrophenyl) amino diphenyl tallization from methanol from which it separates in the form of dark red needles and melts at 162.5-C.

Example 3 Example 7 U Five samples of cotton skeins of five parts each are wet out 111' 1% soap solution, rinsed and passed HCLNHONH O between squeeze rolls.

To uspension of 831 parts f These skeins are treated in individual baths nitrophenyl) amino diphenyl ether in 105 parts containing P naphthol, Darts betaglacial acetic acid at '10" c. is added over a period ethoxy a parts o od hrof 30 minutes a solution of 35.6 parts stannous droxide and Parts Of Water r A hour at chloride dihydrate in 120 parts of concentrated ey a e individually wrun t a are hydrochloric acid. The temperature of the redyed in Separate baths a room temperature 0 action mixture is maintained at 70 C. until ret ning 0.3 pa O t 60101 blend as P p d n duction is complete asis indicated by loss of color. Example 6 dissolved in 200 P s Of W te and The temperature is then lowered and the solution buffered With- Parts O acetic c d a d is made strongly alkaline to phenolphthalein by 15 3 parts of sodium acetate solutions.

addition of 20% sodium hydroxide solution; The Wh n f lly dy d, t e sk ns re cleared at resulting almost white diamine is collected on a 50 C. in a 3% da ash bath, t a in a /2% filter, washed with water, reslurred in dilute sosoap solution at 65 0., rinsed and dried. The dium hydroxide; recollected on a filter and thorskeins are dyed as follows: oughly washed with water. 20

Crystallization from dilute hydrochloric acid A Coupling component Skeln dyeing produces pure 4,4 bis N-(4" aminophenyl) ammo diphenyl ether dihydrocmoride- 2-hydroxy-3-naphtholcacid-(4-chloroenllide)...-. Greenlsh blue.

Bis-(aoetoacetic)-o-tolidlde Golden yellow. Example 4 an droxy carbazole-a-cerboxylic acid-(2'- methylzmllide) ..I. Dark purple. 3.! parts or the diamine dihydrocm r d titiiifiiiii ifffitffliiiffljfijffffP; Green. tamed as described in Example 3 are stirr d t a B-hydroxy-B-naphthoic acid-(2-ethoxyanillde)...- Reddish blue.

smooth paste in60 parts of water. 9 parts of Example 8 N50 OaNa NaOi OrNa 17% hydrochloric acid are added, the tempera- 1.6 parts or the mono-sodium salt of Z-naphture is adjusted at 15 C. and the diamine is 9 thol-3,6-disulfonic acid are dissolved in 80 parts tetrazotized by slow addition of 1.2 parts of soof water containing 1.5 parts of soda ash. This dium nitrite dissolvedin 17 parts of water. 12.9 solution is well stirred at 5 C. and a solution of parts of. salt are added and the separated solid is 0.6 part of the blended tetrazonium chloride prefiltered off. Theresidue is reslurried in 150 parts pared as described in Example 6 dissolved in 15 of water, the temperature raised to 45 C. and 45 parts of water is slowly dropped in. An immethe solution is clarified in the presence of dediate precipitation of a deep blue-black solid colorizing carbon. From the solution by addiforms. a

tion of parts of salt, a light brown precipitate Thedyestufi is filtered oil and dried at 40 C.

forms which is collected on a filter and is washed His 9. dark powder, soluble in water, its aqueous with 5% salt solution. solutions exhibiting a strong .blue fluorescence.

Example 9 on: a on:

, The golden brown tetrazo salt is dried at low 1.5 parts of 1-(4'-sulfophenyl) -3-methyl-5- temperature and is readily soluble in water. pyrazolone are dissolved in 80 parts of water con- Emmpze 6 taining 1.5 parts of soda ash. The solution is chilled and stirred while there is dropped in a 3.0 parts of the tetrazonium chloride obtained solution of 0.6 part. of the blended tetrazonium as described in Example 5 are intimately mixed chloride prepared as in Example 6 dissolved in 15 by blending with 2.9 parts of magnesium sulparts of water. 5 parts of salt are added and the fate-dihydrate and 0.9 part of anhydrous sodium reddish brown precipitate is filtered 011 and is sulfate. dried at 40 C.

This color blend is completely stable to storage A wn p w r is O d which is $0111- and is readily soluble in water. ble in water.

We claim: 1. Compounds having the formula:

smegma.

in which Y is a, member of the group consisting of hydrogen, sulfonic acid and salts of sulfonic acid.

2. A chemical compound having the formula:

U U U U 3. In the method of preparing a 4,4'-bis-amino phenyl amino diphenyl ether the step which com- 

